Department of Chemistry , University of Iowa , Iowa City , Iowa 52245 , United States.
J Am Chem Soc. 2018 Apr 11;140(14):4940-4944. doi: 10.1021/jacs.8b01775. Epub 2018 Mar 27.
Enlargement of a self-assembled metal-organic rhomboid is achieved via the organic solid state. The solid-state synthesis of an elongated organic ligand was achieved by a template directed [2 + 2] photodimerization in a cocrystal. Initial cocrystals obtained of resorcinol template and reactant alkene afforded a 1:2 cocrystal with the alkene in a stacked yet photostable geometry. Cocrystallization performed in the presence of excess template resulted in a 3:2 cocrystal composed of novel discrete 10-component hydrogen-bonded "superassemblies" wherein the alkenes undergo a head-to-head [2 + 2] photodimerization. Isolation and reaction of elongated photoproduct with Cu(II) ions afforded a metal-organic rhomboid of nanoscale dimensions that hosts small molecules in the solid state as guests.
通过有机固态实现了自组装金属有机菱形的放大。通过在共晶中模板导向的[2+2]光二聚反应，实现了拉长有机配体的固态合成。最初获得的间苯二酚模板和反应物烯烃的共晶提供了一个 1:2 的共晶，其中烯烃以堆叠但光稳定的几何形状存在。在过量模板存在下进行共晶化导致形成由新颖离散的 10 组分氢键“超组装体”组成的 3:2 共晶，其中烯烃经历头对头[2+2]光二聚反应。拉长光产物与 Cu(II)离子的分离和反应提供了纳米尺度的金属有机菱形，在固态中作为客体容纳小分子。
